Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/0053—Details of the reactor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
  • C08G65/4056—(I) or (II) containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4087—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the catalyst used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
  • C08G75/23—Polyethersulfones
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00027—Process aspects
  • B01J2219/00033—Continuous processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00027—Process aspects
  • B01J2219/0004—Processes in series
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
  • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK

Definitions

• the present invention relates to a method for continuously producing an aromatic polyether.
• Aromatic polymers such as polyphenylsulfone (PPSU), polysulfone (PSU), polyethersulfone (PES), polyether ether ketone (PEEK), polyether nitrile (PEN), and polyether imide (PEI) excel in heat resistance, chemical resistance, flame retardancy, mechanical strength, electrical characteristics, and dimensional stability. These aromatic polymers can be molded into various molded products, films, sheets, and fibers, etc. through ordinary melt processing methods such as extrusion molding, injection molding, and compression molding, and therefore are commonly used in a wide variety of technical fields including electric devices, electronic devices, automobile instruments, and packaging materials.
• PPSU polyphenylsulfone
• PSU polysulfone
• PES polyethersulfone
• PEEK polyether ether ketone
• PEN polyether nitrile
• PEI polyether imide
• Patent Document 1 describes a method for producing PAEK through a nucleophilic substitution reaction using an aromatic dihalide component, an aromatic dihydroxy component, an alkali metal carbonate or bicarbonate, and a solvent.
• Patent Document 1 JP 61-10486 B
• Polymers are generally produced through a batch process or a continuous process.
• the raw materials and the like are supplied into a continuous production apparatus in a liquid form.
• the polyethers have been produced using a batch process.
• a polymerization reaction through a nucleophilic substitution reaction is inhibited, and therefore it is desirable to not use water in the supply of the raw materials.
• an object of the present invention is to establish a production method through which clogging of piping in a continuous production apparatus is suppressed, and an aromatic polyether can be stably obtained.
• a method for continuously producing an aromatic polyether according to the present invention includes:
• clogging of piping in the continuous production apparatus is suppressed, and an aromatic polyether can be stably obtained.
• An aromatic polyether obtained by the method for continuously producing an aromatic polyether according to the present embodiment is an aromatic polymer in which at least an aromatic ring and an ether group are linked, and includes, in addition to such aromatic polymers, an aromatic polymer containing a sulfone group and/or ketone group, and the like, as well as a nitrile group or the like.
• the continuous production method of the present embodiment is suitable for the production of, amongst aromatic polyethers, polyaryletherketones (aromatic polyether ketones, PAEK), aromatic polysulfones (PASF), and aromatic polyether nitriles (PAEN).
• the aromatic polyether when the aromatic polyether has a plurality of groups selected from a sulfone group, a ketone group, and a nitrile group, the aromatic polyether is classified as an aromatic polymer of the group having a larger number of moles. Specifically, for a case in which the aromatic polyether has both a sulfone group and a ketone group, when the number of moles of the ketone group is greater than the number of moles of the sulfone group, the aromatic polyether is classified as a PAEK, and when the number of moles of the ketone group is less than the number of moles of the sulfone group, the aromatic polyether is classified as a PASF.
• a PAEK obtained by the continuous production method of the present embodiment is not particularly limited, and has a structure made up of repeating units that include a divalent aromatic group (a residue obtained by removing two hydrogen atoms bonded to the aromatic ring from the aromatic compound), a carbonyl group and an ether group.
• Examples of the PAEK include polyether ether ketone (PEEK), polyether ketone (PEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), and polyether ketone ether ketone ketone (PEKEKK).
• a PASF obtained by the continuous production method of the present embodiment is typically a resin having repeating units that include a divalent aromatic group (a residue obtained by removing two hydrogen atoms bonded to the aromatic ring from the aromatic compound) and a sulfonyl group
• PASF polysulfone
• PPSU polyphenylsulfone
• PES polyethersulfone
• a PAEN obtained by the continuous production method of the present embodiment is typically a resin that has repeating units that include a divalent aromatic group having a cyano group bonded thereto (a residue obtained by removing two hydrogen atoms bonded to the aromatic ring from an aromatic compound to which a cyano group is bonded) and an ether group (-O-).
• Examples of the PAEN include polyether nitrile (PEN).
• the continuous production method of the present embodiment is particularly suitable for production of PAEK, PSU, PPSU, PES, and PAEN, which can be obtained by a polycondensation reaction accompanied by the production of byproducts, that is, a desalting polycondensation reaction.
• the weight average molecular weight (Mw) of the aromatic polyether obtained by the continuous production method of the present embodiment is in a wide range.
• a lower limit of the weight average molecular weight of the aromatic polymer obtained through the present embodiment according to gel permeation chromatography (GPC) is at least 3000, preferably at least 5000, and more preferably at least 10000.
• the upper limit of the weight average molecular weight is not greater than 300000, and preferably not greater than 200000.
• the Mw is a polystyrene equivalent value
• the solvent, the column, the measurement temperature, and the like may be selected, as appropriate, according to the type of aromatic polyether of interest.
• the weight average molecular weight is measured using GPC under the following conditions.
• the weight average molecular weight is measured using GPC under the following conditions.
• the following supply step, polymerizing step, and movement step are implemented simultaneously in a continuous production apparatus in which a plurality of reaction vessels are sequentially connected.
• the continuous production apparatus and each of the steps will be explained below.
• the continuous production apparatus Prior to the description of each step, the continuous production apparatus is described first.
• a plurality of reaction vessels are sequentially connected.
• the continuous production apparatus is preferably provided with a housing chamber that houses a plurality of reaction vessels, the reaction vessels are sequentially connected, and the reaction vessels communicate with each other through a gas phase in the housing chamber.
• the continuous production apparatus is preferably one in which a plurality of independent reaction vessels are sequentially connected vertically downward, and the gas phase parts of the reaction vessels are communicated with each other through a ventilation unit.
• the number of reaction vessels is preferably three or more.
• the number of reaction vessels is preferably not greater than 30 and more preferably not greater than 20.
• the preferred continuous production apparatus may be a continuous production apparatus having a configuration similar to that of a continuous production apparatus for a polyarylene sulfide disclosed in, for example, WO 2017/179327 and WO 2018/159220 .
• the gas phase parts of the plurality of reaction vessels are in mutual communication, and therefore the pressure in each of the gas phase parts is uniform.
• water can be removed from any of the plurality of reaction vessels through a water removing unit connected to the continuous production apparatus, and therefore the amount of water in the reaction mixture decreases from the upstream side to the downstream side in the movement direction of the reaction mixture. As a result, reaction inhibition by water is suppressed, and the polymerization reaction is promoted.
• the polymerization solvent, the alkali metal compound, and the raw material are supplied into the continuous production apparatus described above.
• polymerization solvent examples include N,N-dialkylformamides such as N,N-dimethylformamide (DMF), N,N-diethylformamide, and N,N-dipropylformamide; N,N-dialkylacetamides such as N,N-dimethylacetamide, N,N-diethylacetamide, and N,N-dipropylacetamide; N-alkyl-2-pyrrolidones such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; N,N'-dialkylimidazolidinones such as N,N'-dimethylimidazolidinone, N,N'-diethylimidazolidinone, and N,N'-dipropylimidazolidinone; N-alkyl caprolactams such as
• a polymerization solvent selected from the group consisting of N-alkyl-2-pyrrolidone, N-alkylcaprolactam, N, N'-dialkylimidazolidinone, N-alkylcaprolactam, sulfone, and mixtures thereof is preferably used, a polymerization solvent selected from the group consisting of N-alkyl-2-pyrrolidone, sulfone, and mixtures thereof is more preferably used, and a polymerization solvent selected from the group consisting of sulfolane, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, and mixtures thereof is even more preferably used.
• the alkali metal compound may be any compound capable of converting the aromatic dihydroxy compound described below to an alkali metal salt.
• examples of the alkali metal compound include carbonates, hydrogen carbonates, or hydroxides of lithium, sodium, potassium, rubidium, or cesium.
• the alkali metal compound is preferably a sodium or potassium compound, and a carbonate of an alkali metal is also preferable. Sodium carbonate and potassium carbonate are more preferable as the alkali metal compound.
• One type of these alkali metal compounds may be used alone, or two or more types thereof may be used in combination, as appropriate.
• the usage amount of the alkali metal compound is appropriately selected in a range from 1.01 to 2.5 equivalents per equivalent of the aromatic dihydroxy compound that is used. Note that for the aromatic dihydroxy compound and the alkali metal carbonate, one mole corresponds to two equivalents, and for the alkali metal hydrogen carbonate and the hydroxide, one mole corresponds to one equivalent.
• the alkali metal compound is supplied to the continuous production apparatus as an aqueous mixture, that is, as its mixture with water that exhibits fluidity.
• a water-insoluble raw material may be supplied as a mixture with the polymerization solvent into the continuous production apparatus separately from the aqueous mixture.
• the aqueous mixture may contain raw materials such as monomers described below.
• clogging of the piping in the continuous production apparatus and solidification of the raw materials or the like in the continuous production apparatus can be suppressed by supplying the alkali metal compound as an aqueous mixture.
• clogging of the piping can be further suppressed by supplying the aqueous mixture into the continuous production apparatus separately from a mixture of the polymerization solvent and a portion of the raw material that is water insoluble.
• the aqueous mixture include an aqueous slurry and an aqueous solution, and an aqueous solution is preferable.
• raw materials include aromatic dihalogen compounds and aromatic dihydroxy compounds, which are monomers of aromatic polyethers.
• the raw material is supplied in a liquid form, but from the perspectives of quantitative determination and liquid feeding, the raw material is preferably supplied into the continuous production apparatus in the form of a solution obtained by dissolving the raw material in the polymerization solvent.
• the term liquid refers to a solution, a dispersion, or a slurry.
• the term solution indicates a state in which the solid is dissolved in a solvent in a homogeneous state.
• the solvent may be an aqueous solvent such as water, an organic solvent, or a mixture thereof.
• the raw material When the raw material is supplied in the form of a solution, if water is included in the solution of the polymerization solvent and the raw material, at least part of the raw material may be dehydrated and then supplied into the continuous production apparatus.
• the PAEK can be produced using the raw materials described in, for example, JP 61-10486 B , JP 07-138360 A , WO 2003/050163 , JP 2010-70657 A , and JP 2014-532109 T .
• aromatic dihalogen compound examples include, but are not limited to aromatic dihalide compounds (for example, dihalogenated benzophenones) having, per aromatic molecule, an aromatic ring, a ketone group (-CO-), and two halogen groups, such as, for example, 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone.
• aromatic dihalide compounds for example, dihalogenated benzophenones
• -CO- ketone group
• two halogen groups such as, for example, 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone.
• aromatic dihydroxy compound examples include 1,3-dihydroxybenzene (resorcin), 1,4-dihydroxybenzene (hydroquinone), 4,4'-dihydroxybiphenyl (4,4'-biphenol), 4,4'-dihydroxy-terphenyl, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybenzophenone, and 4,4'-tetraphenyl-bisphenol, but the aromatic dihydroxy compound is not limited to these, and various diphenols such as bisphenol A, for example, can be used in addition to these.
• a compound having, per molecule, an aromatic ring, a ketone group (-CO-), a halogen group, and a hydroxyl group can be subjected to the same polycondensation reaction.
• compounds that can be used in this reaction include compounds such as 4-hydroxy-4'-fluorobenzophenone and 4-hydroxy-4'-chlorobenzophenone.
• the aromatic dihalogen compound is preferably mixed with the polymerization solvent and supplied into the continuous production apparatus.
• the alkali metal compound and the aromatic dihydroxy compound are preferably mixed with water and supplied as an aqueous mixture such as an aqueous solution. This is because the activity of the aromatic dihydroxy compound for the polymerization reaction increases due to a neutralization reaction between the alkali metal compound and the aromatic dihydroxy compound. Thereby, the reaction of the aromatic dihydroxy compound with the aromatic dihalogen compound can be initiated quickly after fed into the continuous production apparatus, and a high molecular weight PAEK can be obtained.
• the alkali metal compound and the aromatic dihydroxy compound are mixed with water and supplying them as an aqueous mixture such as an aqueous solution, the alkali metal compound does not precipitate in clump forms in the continuous production apparatus, and the load on the continuous production apparatus can be suppressed.
• the aromatic polyether to be produced is PASF
• the PASF can be produced using the raw materials described in JP 2013-159641 A , for example.
• aromatic dihalogen compound examples include aromatic dihalogenosulfone compounds such as bis(4-chlorophenyl)sulfone (also referred to as dichlorodiphenylsulfone) and 4,4'-bis(4-chlorophenylsulfonyl)biphenyl.
• aromatic dihalogenosulfone compound may be a compound having an aromatic ring, a sulfonyl group (-SO 2 -), and two halogen groups per molecule.
• aromatic dihydroxy compound examples include bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone, and bis(4-hydroxy-3-phenylphenyl) sulfone, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) hexafluoropropane, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxy-3-methylphenyl) sulfide, bis(4-hydroxyphenyl) ether, hydroquinone, resorcin, catechol, phenylhydroquinone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3,5,3',5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,2'-diphenyl-4,4'-dihydroxybiphenyl, and 4,4'-dihydroxy-p
• the aromatic dihydroxy compound may be a compound having an aromatic ring and two hydroxyl groups per molecule.
• a compound having a halogeno group and a hydroxyl group per molecule such as 4-hydroxy-4'-(4-chlorophenylsulfonyl) biphenyl, can be used in place of all or some of the aromatic dihalogen sulfone compound and the aromatic dihydroxy compound.
• a compound having, per molecule, an aromatic ring, a sulfonyl group (-SO 2 -), a halogen group, and a hydroxyl group can be subjected to the same polycondensation reaction.
• compounds that can be used in this reaction include compounds such as 4-(4-fluorobenzenesulfonyl) phenol and 4-(4-chlorobenzenesulfonyl) phenol.
• the PAEN can be produced using the raw materials described in JP 07-138360 A , for example.
• the PAEN of the present invention is produced by using, as known raw material monomers, an aromatic dihalide compound and an aromatic dihydroxy compound, and subjecting them to desalting polycondensation in a polymerization solvent along with an alkali metal carbonate, an alkali metal hydrogen carbonate, or an alkali metal hydroxide, which are basic alkali metal compounds capable of forming a phenolate-type salt with the aromatic dihydroxy compound.
• aromatic dihalide compound examples include, but is not limited to, 2,6-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2,4-difluorobenzonitrile, and 2,4-dichlorobenzonitrile.
• aromatic dihydroxy compound a compound given as an example of a raw material for the PAEK described above can be used.
• a compound having, per molecule, a halogen group, a hydroxyl group, and an aromatic ring with a nitrile group can be subjected to the same polycondensation reaction.
• the compound that can be used in this reaction include compounds such as 2-hydroxy-6-fluorobenzonitrile, 2-hydroxy-6-chlorobenzonitrile, 2-hydroxy-4-fluorobenzonitrile, and 2-hydroxy-4-chlorobenzonitrile.
• the continuous production apparatuses disclosed in WO 2017/179327 and WO 2018/159220 have three raw material supply lines each.
• the aqueous solution of the alkali metal compound and the raw materials are preferably supplied from at least two supply lines including a line for supplying the aqueous solution of the alkali metal compound and another line for supplying the raw materials.
• the supply amount of the polymerization solvent, the alkali metal compound, and the raw materials to be supplied into the continuous production apparatus can be appropriately changed depending on factors such as the volume of the continuous production apparatus and the intended production volume.
• aromatic polyether of interest depending on the type of aromatic polyether of interest, with regard to each of the aromatic dihalogen compound, the aromatic dihydroxy compound, and the aromatic compound having a halogen group and a hydroxyl group, one type may be used alone, or two or more types may be used in combination.
• the molar ratio of hydroxyl groups to halogen groups is an important factor that determines the degree of polymerization.
• the number of moles of the aromatic dihydroxy compound per one mole of the aromatic dihalogen compound supplied into the continuous production apparatus is preferably from 0.90 to 1.10, more preferably from 0.92 to 1.08, and even more preferably from 0.94 to 1.06.
• n is an integer of 1 or greater
• the number of moles of the bases per mole of the aromatic dihydroxy compound may be adjusted so that a total of values obtained by multiplying by n/2 for each type of base is preferably from 0.95 to 1.15, and more preferably from 1.00 to 1.10.
• the n is 2 when the base is sodium carbonate, and is 1 when the base is sodium hydrogen carbonate or sodium hydroxide.
• the reaction mixture is formed by carrying out a polymerization reaction in the polymerization solvent in at least one or more reaction vessels.
• the polymerization reaction carried out in the continuous production method of the present embodiment is typically a desalting polycondensation reaction through an aromatic nucleophilic substitution reaction.
• the polymerization temperature is preferably greater than 100°C and not greater than 320°C, more preferably from 150°C to 300°C, and even more preferably from 170°C to 280°C.
• the polymerization temperature is preferably greater than 100°C and not greater than 290°C, more preferably from 150°C to 270°C, and even more preferably from 170°C to 250°C.
• the polymerization temperature is the temperature under pressurized conditions.
• the polymerization reaction is carried out at a gage pressure of greater than 0 MPa to not greater than 1.0 MPa, preferably not greater than 0.7 MPa, and more preferably not greater than 0.5 MPa. From perspectives of promoting the polymerization reaction, the pressure of each reaction vessel of the continuous production apparatus is preferably uniform.
• the pH of the reaction mixture in the at least one or more reaction vessels is preferably from 9 to 12.5, more preferably from 9.5 to 12, and even more preferably from 10 to 11.5.
• the pH can be adjusted by, for example, changing the usage amount of the alkali metal compound, and can be adjusted by adding a strong base such as sodium hydroxide and potassium hydroxide to an aqueous solution of the alkali metal compound.
• the reaction mixture includes the aromatic polyether having a weight average molecular weight from 2000 to 50000, and the pH of the reaction mixture in at least one of the at least one reaction vessel is preferably from 9 to 12.5, more preferably from 9.5 to 12, and even more preferably from 10 to 11.5. That is, when the pH of the reaction mixture containing the aromatic polyether in the polymerization reaction is within the range described above, a high molecular weight aromatic polyether is obtained. When the pH is lower than the abovementioned range in all the reaction vessels, the polymerization reaction does not proceed, and when the pH is higher than the abovementioned range, a undesirable side reaction occurs, and a high molecular weight aromatic polyether cannot be obtained.
• reaction mixture is sequentially moved to each reaction vessel. That is, while the polymerization reaction proceeds, the reaction mixture moves sequentially through the plurality of sequentially connected reaction vessels.
• the continuous production method of the present embodiment may include other steps in addition to the supply, polymerizing, and movement steps. Examples of other steps include a collection step of collecting the reaction mixture.
• the supply step, polymerizing step, movement step, and collection step are preferably performed simultaneously.
• the reaction mixture When collecting the reaction mixture, the reaction mixture is preferably collected in a slurry state by controlling the mass ratio of the raw material monomers to the polymerization solvent.
• the mass ratio of the monomer/polymerization solvent is ordinarily from 1 to 25 parts by mass, preferably from 3 to 20 parts by mass, and more preferably from 5 to 15 parts by mass, per 100 parts by mass of the polymerization solvent.
• the polymerization solvent may be supplied from the middle of the polymerization reaction until the reaction mixture is collected, and preferably from after the completion of the polymerization reaction until the reaction mixture is collected, such that the mass ratio of the raw material monomer/polymerization solvent is within the range described above.
• the mass ratio of the monomers to the polymerization solvent in the range described above, the problem of solidification of the reaction mixture during the collection of the reaction mixture can be resolved.
• the obtained aromatic polyether can be easily washed and the polymerization solvent and the like can be easily collected or recycled.
• the method for continuously producing an aromatic polyether includes simultaneously implementing: a supply step of supplying a polymerization solvent, an alkali metal compound, and a raw material into a continuous production apparatus in which a plurality of reaction vessels are sequentially connected; a polymerizing step of forming a reaction mixture by carrying out a polymerization reaction in the polymerization solvent in at least one or more of the reaction vessels; and a movement step of sequentially moving the reaction mixture to each reaction vessel; and supplying the alkali metal compound as an aqueous mixture.
• the aqueous mixture containing at least the alkali metal compound is preferably supplied into the continuous production apparatus separately from a mixture containing at least part of the raw material and the polymerization solvent.
• the raw material is preferably in the form of a solution in which the raw material is dissolved in the polymerization solvent.
• the pH of the reaction mixture in at least one or more of the reaction vessels is preferably from 9 to 12.5.
• the reaction mixture in at least one of the reaction vessels, preferably includes the aromatic polyether having a weight average molecular weight from 2000 to 50000, and the pH of the reaction mixture in at least one of the at least one reaction vessel is preferably from 9 to 12.5.
• the method for continuously producing an aromatic polyether according to the present embodiment preferably includes an aromatic dihalogen compound and an aromatic dihydroxy compound as the raw materials.
• the method for continuously producing an aromatic polyether according to the present embodiment preferably includes an alkali metal carbonate in the alkali metal compound.
• the aromatic polyether is preferably a polyaryletherketone.
• the polyaryletherketone is preferably polyether ether ketone.
• the aromatic polyether is preferably an aromatic polysulfone.
• the aromatic polysulfone is preferably a polysulfone, a polyphenylsulfone, or a polyethersulfone.
• an aromatic dihalogen compound and an aromatic dihydroxy compound are preferably contained as raw materials, and the alkali metal compound and the aromatic dihydroxy compound are preferably mixed with water and supplied as the aqueous mixture.
• the continuous production apparatus is preferably provided with a housing chamber that houses a plurality of reaction vessels, and preferably, the reaction vessels are sequentially connected, and are in communication with each other through a gas phase in the housing chamber.
• a polymerization reaction was carried out using a continuous production apparatus having six reaction vessels formed by partitioning a housing chamber with five partition walls as shown in FIG. 1 of WO 2018/159220 .
• This continuous production apparatus was a reactor made of SUS having an inner diameter of 108 mm and a length of 300 mm with the partition walls being semicircular.
• the continuous production apparatus was charged with 950 g of N-methyl-2-pyrrolidone (NMP). Subsequently, while nitrogen gas was flowed at a flow rate of 0.1 NL/min from an upstream side to a downstream side of the fifth partition wall, an external heater installed at a bottom portion of a housing chamber 2 was used to maintain a temperature 1 of a portion delimited by the first partition wall and the second partition wall from the upstream side, that is, the temperature 1 of a second reaction vessel from the upstream side, at 230°C, and to maintain a temperature 2 of a fifth reaction vessel from the upstream side at 260°C, and to maintain a temperature 3 of a sixth reaction vessel from the upstream side at 260°C.
• NMP N-methyl-2-pyrrolidone
• a temperature 4 of the first reaction vessel from the upstream side was 190°C
• a temperature 5 of the fourth reaction vessel from the upstream side was 255°C.
• a solution of NMP and 4,4'-difluorobenzophenone (DFBP) was continuously supplied at a rate of 5.3 g/min
• an aqueous solution of water, hydroquinone (HQ), and sodium carbonate was continuously supplied at a rate of 9.2 g/min, the solutions being supplied through separate supply lines for 6 hours using a constant-flow pump.
• PEEK which was the reaction product
• the reaction mixture was added dropwise to five times the amount of water, and the reaction product was precipitated and filtered. The reaction product was then washed with methanol and filtered. The obtained cake was dried in a vacuum at 60°C for 8 hours, and PEEK powder was obtained. The weight average molecular weight of this PEEK powder was measured under the conditions described above using the GPC-104 gel permeation chromatograph (GPC) from Shodex.
• GPC GPC-104 gel permeation chromatograph
• the weight average molecular weight was 65000 for the PEEK powder sampled from the reaction mixture collection line, 12000 for the PEEK powder sampled from the third reaction vessel, 24000 for the PEEK powder sampled from the fourth reaction vessel, 42000 for the PEEK powder sampled from the fifth reaction vessel, and 62000 for the PEEK powder sampled from the sixth reaction vessel.
• the pH of the reaction solution in each reaction vessel was measured at 23°C using the SK-640PH pH meter available from Sato Keiryoki Mfg. Co., Ltd., and was found to be 10.1 in the third reaction vessel, 9.8 in the fourth and fifth reaction vessels, and 9.0 in the sixth reaction vessel.
• the pH of the reaction mixture sampled from the reaction mixture collection line was 9.7. Note that the weight average molecular weight was determined by the method described above.
• a continuous production apparatus similar to the apparatus used in Example 1 was charged with 950 g of N-methyl-2-pyrrolidone (NMP). Subsequently, while nitrogen gas was flowed at a flow rate of 0.1 NL/min from an upstream side to a downstream side of the fifth partition wall, an external heater installed at a bottom portion of the housing chamber 2 was used to maintain the temperature 1 of a portion delimited by the first partition wall and the second partition wall from the upstream side, that is, the temperature 1 of the second reaction vessel from the upstream side, at 210°C, and to maintain the temperature 2 of the fifth reaction vessel from the upstream side at 230°C, and to maintain the temperature 3 of the sixth reaction vessel from the upstream side at 230°C.
• NMP N-methyl-2-pyrrolidone
• the temperature 4 of the first reaction vessel from the upstream side was 170°C
• the temperature 5 of the fourth reaction vessel from the upstream side was 225°C.
• a solution of NMP and 4,4'-dichlorodiphenylsulfone (DCDPS) was continuously supplied at a rate of 2.2 g/min
• an aqueous solution of water, NMP, 4,4'-biphenol, sodium hydroxide, and sodium carbonate was continuously supplied at a rate of 6.5 g/min, the solutions being supplied through separate supply lines for 7 hours using a constant-flow pump.
• NMP:DCDPS (weight ratio) 352.48:201.01
• DCDPS:4,4'-biphenol (molar ratio) 1.01:1
• 4,4'-biphenol:sodium hydroxide:sodium carbonate (molar ratio) 1:1.8:0.15
• water:NMP:4,4'-biphenol (weight ratio) 1025.90:407.74:129.06.
• the reaction product was sampled for analysis from the reaction mixture collection line.
• the reaction mixture was added dropwise to five times the volume of water, the product was precipitated and filtered, and then further washed with methanol and filtered, the obtained cake was dried in a vacuum at 60°C for 8 hours, and PPSU powder was obtained.
• the PPSU powder had a weight average molecular weight Mw, calibrated with polystyrene and obtained through GPC, of 36000.
• the weight average molecular weight was 10000 for the PPSU powder sampled from the third reaction vessel, 20000 for the PPSU powder sampled from the fourth reaction vessel, 37000 for the PPSU powder sampled from the fifth reaction vessel, and 39000 for the PPSU powder sampled from the sixth reaction vessel.
• the pH of the reaction solution in each reaction vessel was measured at 23°C using the SK-640PH pH meter available from Sato Keiryoki Mfg. Co., Ltd., and was found to be 10.1 in the third reaction vessel, 10.3 in the fourth and fifth reaction vessels, and 9.6 in the sixth reaction vessel. Further, the pH of the reaction mixture sampled from the reaction mixture collection line was 7.8.
• a continuous production apparatus similar to the apparatus used in Example 1 was charged with 950 g of N-methyl-2-pyrrolidone (NMP). Subsequently, while nitrogen gas was flowed at a flow rate of 0.1 NL/min from an upstream side to a downstream side of the fifth partition wall, an external heater installed at a bottom portion of the housing chamber 2 was used to maintain the temperature 1 of a portion delimited by the second partition wall and the third partition wall from the upstream side, that is, the temperature 1 of the third reaction vessel from the upstream side, at 200°C, and to maintain the temperature 2 of the fifth reaction vessel from the upstream side at 220°C, and to maintain the temperature 3 of the sixth reaction vessel from the upstream side at 220°C.
• NMP N-methyl-2-pyrrolidone
• the temperature 4 of the first reaction vessel from the upstream side was 150°C
• the temperature 5 of the fourth reaction vessel from the upstream side was 215°C.
• a solution of NMP and 4,4'-dichlorodiphenylsulfone (DCDPS) was continuously supplied at a rate of 3.5 g/min
• an aqueous solution of water, 4,4'-dihydroxydiphenylsulfone (bisphenol S), and sodium hydroxide was continuously supplied at a rate of 6.4 g/min, the solutions being supplied through separate supply lines for 11 hours using a constant-flow pump.
• the reaction product was collected for analysis from the reaction mixture collection line.
• the reaction mixture was added dropwise to five times the volume of water, the product was precipitated and filtered, and then further washed with methanol and filtered, the obtained cake was dried in a vacuum at 60°C for 8 hours, and PES powder was obtained.
• the PES powder had a weight average molecular weight Mw, calibrated with polystyrene and obtained through GPC, of 14000.
• the weight average molecular weight was 5000 for the PES powder sampled from the third reaction vessel, 5000 for the PES powder sampled from the fourth reaction vessel, 6000 for the PES powder sampled from the fifth reaction vessel, and 14000 for the PES powder sampled from the sixth reaction vessel.
• the pH of the reaction solution in each reaction vessel was measured at 23°C using the SK-640PH pH meter available from Sato Keiryoki Mfg. Co., Ltd., and was found to be 11.0 in the third reaction vessel, 11.1 in the fourth reaction vessel, 11.0 in the fifth reaction vessel, and 10.1 in the sixth reaction vessel. Further, the pH of the reaction mixture sampled from the reaction mixture collection line was 10.2.
• a continuous production apparatus similar to the apparatus used in Example 1 was charged with 950 g of N-methyl-2-pyrrolidone (NMP). Subsequently, while nitrogen gas was flowed at a flow rate of 0.1 NL/min from an upstream side to a downstream side of the fifth partition wall, an external heater installed at a bottom portion of the housing chamber 2 was used to maintain the temperature 1 of a portion delimited by the second partition wall and the third partition wall from the upstream side, that is, the temperature 1 of the third reaction vessel from the upstream side, at 200°C, and to maintain the temperature 2 of the fifth reaction vessel from the upstream side at 210°C, and to maintain the temperature 3 of the sixth reaction vessel from the upstream side at 210°C.
• NMP N-methyl-2-pyrrolidone
• the temperature 4 of the first reaction vessel from the upstream side was 170°C
• the temperature 5 of the second reaction vessel from the upstream side was 190°C
• the temperature 6 of the fourth reaction vessel from the upstream side was 205°C.
• a solution of NMP and 4,4'-dichlorodiphenylsulfone (DCDPS) and 4,4'-biphenol was continuously supplied at a rate of 4.3 g/min
• an aqueous solution of water, sodium hydroxide, and sodium carbonate was continuously supplied at a rate of 1.2 g/min, the solutions being supplied through separate supply lines for 7 hours using a constant-flow pump.
• the reaction product was sampled for anlysis from the reaction mixture collection line.
• the reaction mixture was added dropwise to five times the volume of water, the product was precipitated and filtered, and then further washed with methanol and filtered, the obtained cake was dried in a vacuum at 60°C for 8 hours, and PPSU powder was obtained.
• the PPSU powder had a weight average molecular weight Mw, calibrated with polystyrene and obtained through GPC, of 11000.
• the weight average molecular weight was 7000 for the PPSU powder sampled from the third reaction vessel, 10000 for the PPSU powder sampled from the fourth reaction vessel, 13000 for the PPSU powder sampled from the fifth reaction vessel, and 14000 for the PPSU powder sampled from the sixth reaction vessel.
• the pH of the reaction solution in each reaction vessel was measured at 23°C using the SK-640PH pH meter available from Sato Keiryoki Mfg. Co., Ltd., and was found to be 10.2 in the third reaction vessel, 10.5 in the fourth and fifth reaction vessels, and 10.0 in the sixth reaction vessel. Further, the pH of the reaction mixture sampled from the reaction mixture collection line was 10.0.
• a continuous production apparatus similar to the apparatus used in Example 1 was charged with 950 g of N-methyl-2-pyrrolidone (NMP). Subsequently, while nitrogen gas was flowed at a flow rate of 0.1 NL/min from an upstream side to a downstream side of the fifth partition wall, an external heater installed at a bottom portion of the housing chamber 2 was used to maintain the temperature 1 of a portion delimited by the first partition wall and the second partition wall from the upstream side, that is, the temperature 1 of the second reaction vessel from the upstream side, at 230°C, and to maintain the temperature 2 of the fifth reaction vessel from the upstream side at 260°C, and to maintain the temperature 3 of the sixth reaction vessel from the upstream side at 260°C.
• NMP N-methyl-2-pyrrolidone
• a temperature 4 of the first reaction vessel from the upstream side was 190°C
• a temperature 5 of the fourth reaction vessel from the upstream side was 255°C.
• the temperature 1 at a portion delimited by the second partition wall that is, the temperature 1 of the second reaction vessel from the upstream side
• the temperature 2 at a portion delimited by the third partition wall and the fourth partition wall that is, the temperature 2 of the fourth reaction vessel from the upstream side
• the temperature 3 of a portion delimited by the fifth partition wall from the upstream side and a side wall of the housing chamber 2 that is, the temperature 3 of the sixth reaction vessel from the upstream side
• the potassium carbonate having an average particle size of not less than 95 ⁇ m in solution was pulverized (to an average particle size of not greater than 95 ⁇ m) into a slurry using a homogenizer at a speed of approximately 10000 rpm/min.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyethers (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=71521261

Family Applications (1)

Country Status (6)

Families Citing this family (1)

Family Cites Families (14)

• 2019
  • 2019-12-12 EP EP19908545.7A patent/EP3910002A4/fr not_active Withdrawn
  • 2019-12-12 KR KR1020217024565A patent/KR20210111806A/ko not_active Abandoned
  • 2019-12-12 JP JP2020565648A patent/JP7118174B2/ja not_active Expired - Fee Related
  • 2019-12-12 CN CN201980080360.8A patent/CN113166397A/zh active Pending
  • 2019-12-12 US US17/309,924 patent/US20220089815A1/en not_active Abandoned
  • 2019-12-12 WO PCT/JP2019/048645 patent/WO2020145017A1/fr not_active Ceased

Also Published As

Similar Documents

Legal Events